In this paper, imidazole-based ionic liquids with different alkyl chains were covalently grafted onto calixarene, which resulted in the formation of 4–6 with the molecular formula [C44H56O4·2C4H6N2(CH2)n]·2Br [n = 5 (4), n = 8 (5), n = 12 (6)]. Ion exchange of 4–6 with Na9EuW10O36·32H2O (denoted EuW10) led to the formation of new inorganic–organic hybrid materials 7–9 with a molecular composition of [C44H56O4·2C4H6N2(CH2)n]4.5·EuW10O36·xH2O [n = 5, x = 10 (7); n = 8, x = 7 (8); n = 12, x = 20 (9)]. Contact angles above 139° suggested superhydrophobicity of the resulting hybrid materials 7–9. Sulfur removal of dibenzothiophene by applying hybrid materials 7–9 as heterogeneous catalytic systems indicated that deep desulfurization could be achieved at 70 °C in 7, 5.5, and 5 min, respectively. Hybrid materials 7–9 were demonstrated to be highly efficient and selective desulfurization systems that could be reused more than 10 times without a clear decrease in reactivity.